CN106398193A - High-temperature resistant polyamide 6T/11 composition and preparation method thereof - Google Patents
High-temperature resistant polyamide 6T/11 composition and preparation method thereof Download PDFInfo
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- CN106398193A CN106398193A CN201610855302.6A CN201610855302A CN106398193A CN 106398193 A CN106398193 A CN 106398193A CN 201610855302 A CN201610855302 A CN 201610855302A CN 106398193 A CN106398193 A CN 106398193A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
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- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08K2201/003—Additives being defined by their diameter
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- C08K2201/00—Specific properties of additives
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to a high-temperature resistant polyamide 6T/11 composition and a preparation method thereof. The high-temperature resistant polyamide 6T/11 composition is prepared from the following raw materials including a high-temperature resistant polyamide 6T/11 resin prepolymer, high-temperature resistant polyamide 6T/11 resin, toluene diisocyanate, 2,2'-(1, 3-phenylene)-bisoxazoline, a coupling reagent, alkali-free glass fibers, N,N'-ethylene diste, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,3-benzene dicarboxamide, bis(2,6-di-tert-butyl-4-methyl phenyl)pentaerythritol diphosphate, an anti-dripping agent and simethicone. The high-temperature resistant polyamide 6T/11 composition has the characteristics of high fluidity, high tensile strength and low water absorption, and can be applied to the electronic and electrical product field, the LED field, the automotive field, the aerospace field, the military field and the like.
Description
Technical field
The present invention relates to Material Field, more particularly to a kind of heat resistant polyamide 6T/11 compositionss and preparation method thereof.
Background technology
Heat resistant polyamide is typically by aliphatic diamidogen and aromatic diacid, or aromatic diamidogen and fat
The diacid of race is prepared through polycondensation.Due to introducing phenyl ring on molecular backbone, heat resistant polyamide not only maintains fat
The mechanical property that polyamide has is good, acid and alkali-resistance and the advantages of self lubricity, also overcome that its water absorption rate is high, dimensional stability not
Good shortcoming so as to be particularly well-suited in auto industry, in order to replace the part metals structural member in automobile, to realize light weight
Change it is also possible to be used for manufacturing the insulating body of electronic device, or be used for surface mounting technique.
Industrialized heat resistant polyamide mainly has polyamide 6 T (copolymer), polyamide 9T, polyamide 10T etc..Polyamides
The fusing point of amine 6T resin be 370 DEG C about, it alreadys exceed decomposition temperature, actually can not carry out melt-processed it is necessary to
The monomer adding third component makes the melt temperature of polymer be down to less than 320 DEG C.But, add the Third monomer of low content not
Enough to improve its processing characteristics, and the range of work is too narrow, and adds the Third monomer of high-load can make the molten of copolymer resin
Point is too low, does not reach resistant to elevated temperatures requirement.
For above-mentioned problem, in currently available technology, the modification of polyamide is done with some researchs, such as Chinese patent
CN 103333335A discloses a kind of high fluidity PA10T Amilan polyamide resin composition, and it is obtained by solid phase by two kinds
Different viscositys PA10T polyamide composition；Chinese patent CN 103360599A discloses a kind of high fluidity PA10T
Amilan polyamide resin composition, it is prepared into by the PA10T resin prepolymer being obtained by solid phase and PA10T resin alloy
Arrive；Chinese patent CN 103483809A discloses a kind of high-fluidity polyamide base halogen-free flame-retarded heat-conducting composite, by with
High-fluidity nylon 6 resin containing branched structure is matrix, is simultaneously introduced heat filling, halogen-free flame retardants, antioxidant and idol
The auxiliary agents such as connection agent are prepared for a kind of new halogen-free flame-retarded heat-conducting composite by double-screw melt blending technology；Chinese patent
CN103012955A discloses a kind of high flowing fiberglass reinforced PP/PA composite and preparation method thereof；Chinese patent
CN103724979A discloses a kind of high flowing heatproof LED PPO/PA compositionss and preparation method thereof.
Content of the invention
The present invention be directed to the deficiencies in the prior art are it is therefore an objective to provide one kind to have high fluidity, high tensile and low
The heat resistant polyamide 6T/11 compositionss of water absorption rate, can serve as electrical/electronic components, automobile component, are particularly useful as
The molding substrate material of electronic unit.
For reaching above-mentioned purpose, the present invention adopts below scheme：
A kind of heat resistant polyamide 6T/11 compositionss, said composition is prepared from by the raw material of following weight portion：
The intrinsic viscosity of described heat resistant polyamide 6T/11 resin prepolymer is 0.4～0.6dL/g；
The intrinsic viscosity of described heat resistant polyamide 6T/11 resin is 0.7～1.0dL/g；
Described coupling agent be gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-
Gamma-aminopropyl-triethoxy-silane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-ammonia third
Ylmethyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, aniline first
At least one in ethyl triethoxy silicane alkane；
The length of described alkali-free glass fibre is 2～4mm, a diameter of 9～11 μm；
Described anti-dripping agent is fluoropolymer.
Wherein in some embodiments, heat resistant polyamide 6T/11 compositionss, by the raw material preparation of following weight portion
Become：
Wherein in some embodiments, heat resistant polyamide 6T/11 compositionss, further preferably former by following weight portion
Material is prepared from：
Wherein in some embodiments, the intrinsic viscosity of described heat resistant polyamide 6T/11 resin prepolymer is 0.45～
0.55dL/g；The intrinsic viscosity of described heat resistant polyamide 6T/11 resin is 0.75～0.95dL/g.
Wherein in some embodiments, described coupling agent is gamma-aminopropyl-triethoxy-silane, γ-aminopropyl trimethoxy
At least one in base silane；Described anti-dripping agent is politef.
Wherein in some embodiments, described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11
Resin is formed by monomer 1 and polyesteramide copolymerization, and described monomer 1 is 1 for mol ratio：1：0.45～0.55 hexamethylene diamine, to benzene
Dioctyl phthalate, 11- aminoundecanoic acid, described polyesteramide addition is the 1～8% of described monomer 1 gross weight.
Wherein in some embodiments, described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11
Resin is obtained by following synthetic method：
(1) the described monomer 1 after vacuum drying is added in stirring-type polymer reactor, is simultaneously introduced described polyamide
Ester, and molecular weight regulator, antioxidant, water；Then evacuation 4～6min, logical nitrogen 4～6min, so circulate 5～7 times,
So that reactant is present in the lower environment of nitrogen protection, control in described stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by airtight for described stirring-type polymer reactor constant-speed heating to 272～280 DEG C, adjust institute
The mixing speed stating stirring-type polymer reactor is 30～50r/min, wherein, when described stirring-type polymer reactor temperature reaches
When 215 DEG C, it is deflated to 2.0MPa, and maintains pressure in 2.0MPa, after reacting 1～2 hour, be deflated to normal pressure, be warming up to simultaneously
After continuing reaction at 310～320 DEG C 1～2 hour, obtain described heat resistant polyamide 6T/11 resin prepolymer；
(3) the described heat resistant polyamide 6T/11 resin prepolymer that step (2) obtains persistently is taken out at 310～320 DEG C
After vacuum 0.3～1 hour, obtain described heat resistant polyamide 6T/11 resin；
Described molecular weight regulator is addition is described monomer 1 gross weight 0.1～3% benzoic acid；Described antioxygen
Agent is addition is described monomer 1 gross weight 0.1～0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,
3- benzene diamides；Appropriate amount of water.
It is a further object of the present invention to provide the preparation method of heat resistant polyamide 6T/11 compositionss.
The preparation method of above-mentioned heat resistant polyamide 6T/11 compositionss, specific technical scheme, comprise the following steps：
(1) by described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin (PA6T/11)
It is placed in 80～100 DEG C, after being dried 4～12 hours, cooling, by the heat resistant polyamide 6T/11 resin prepolymer after cooling, resistance to height
Warm polyamide 6 T/11 resin, and described toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline
(PBO), N, N'- double (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- methyl
Phenyl) pentaerythritol diphosphate, anti-dripping agent and dimethicone be added in homogenizer and mixed；
(2) described coupling agent, alkali-free glass fibre and N,N' ethylene bis stearmide are added to another high-speed stirring
Mix in machine and mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the such as the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize,
Technological parameter is as follows：One area's temperature is 260～290 DEG C, and two area's temperature are 290～305 DEG C, and three area's temperature are 295～310 DEG C,
Four area's temperature are 300～310 DEG C, and five area's temperature are 300～310 DEG C, and six area's temperature are 300～310 DEG C, and seven area's temperature are 300
～310 DEG C, eight area's temperature are 300～310 DEG C, and die head temperature is 295～305 DEG C, and screw speed is 200～600rpm.
Wherein in some embodiments, by described heat resistant polyamide 6T/11 resin prepolymer and resistance in described step (1)
High temperature polyamide 6T/11 resin (PA6T/11) is placed in 90 DEG C, is dried 4～6 hours；Technological parameter in described step (3) is：
One area's temperature is 260～285 DEG C, and two area's temperature are 290～300 DEG C, and three area's temperature are 295～305 DEG C, and four area's temperature are 300
～305 DEG C, five area's temperature are 300～305 DEG C, and six area's temperature are 300～305 DEG C, and seven area's temperature are 300～305 DEG C, eight area's temperature
Spend for 300～305 DEG C, die head temperature is 295～300 DEG C, screw speed is 200～400rpm.
Wherein in some embodiments, the screw configuration of described parallel double-screw extruder is single thread；Spiro rod length L
Ratio L/D with diameter D is 35～50；Described screw rod is provided with the gear block area of more than 1 (containing 1) and more than 1 (containing 1)
Left-hand thread area.
Wherein in some embodiments, the ratio L/D of described spiro rod length L and diameter D is 35～45；Described screw rod is provided with
2 gear block areas and 1 left-hand thread area.
Wherein in some embodiments, described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11
Resin is formed by monomer 1 and polyesteramide copolymerization, and described monomer 1 is 1 for mol ratio：1：0.45～0.55 hexamethylene diamine, to benzene
Dioctyl phthalate, 11- aminoundecanoic acid, described polyesteramide addition is the 1～8% of described monomer 1 gross weight.
Wherein in some embodiments, described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11
Resin is obtained by following synthetic method：
(1) the described monomer 1 after vacuum drying is added in stirring-type polymer reactor, is simultaneously introduced described polyamide
Ester, and molecular weight regulator, antioxidant, water；Then evacuation 4～6min, logical nitrogen 4～6min, so circulate 5～7 times,
So that reactant is present in the lower environment of nitrogen protection, control in described stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by airtight for described stirring-type polymer reactor constant-speed heating to 272～280 DEG C, adjust institute
The mixing speed stating stirring-type polymer reactor is 30～50r/min, wherein, when described stirring-type polymer reactor temperature reaches
When 215 DEG C, it is deflated to 2.0MPa, and maintains pressure in 2.0MPa, after reacting 1～2 hour, be deflated to normal pressure, be warming up to simultaneously
After continuing reaction at 310～320 DEG C 1～2 hour, obtain described heat resistant polyamide 6T/11 resin prepolymer；
(3) the described heat resistant polyamide 6T/11 resin prepolymer that step (2) obtains persistently is taken out at 310～320 DEG C
After vacuum 0.3～1 hour, obtain described heat resistant polyamide 6T/11 resin；
Described molecular weight regulator is addition is described monomer 1 gross weight 0.1～3% benzoic acid；Described antioxygen
Agent is addition is described monomer 1 gross weight 0.1～0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,
3- benzene diamides；Appropriate amount of water.
The principle of the present invention is as follows：
In order to solve the processing temperature narrow limits of heat resistant polyamide 6T/11 resin and the defect that processing characteristics is not good,
The present invention to improve the processing characteristics of heat resistant polyamide 6T/11 resin using heat resistant polyamide 6T/11 resin prepolymer, this
It is because that heat resistant polyamide 6T/11 resin prepolymer possesses preferably mobile performance, and heat resistant polyamide 6T/11 resin
Possesses preferably mechanical property.Meanwhile, the strand of the partly relatively low intrinsic viscosity of heat resistant polyamide 6T/11 resin prepolymer
The end group of (intrinsic viscosity is lower, and activity is higher) can respectively with the isocyanate groups of toluene di-isocyanate(TDI), 2,2'- (1,
3- phenylene)-bisoxazoline oxazoline group occur chain extending reaction, the intrinsic viscosity improving such prepolymer is to reasonable model
Enclose, thus reducing the impact to heat resistant polyamide 6T/11 resin mechanical property for such prepolymer, and toluene di-isocyanate(TDI)
Isocyanate groups, 2,2'- (1,3- phenylene)-bisoxazoline oxazoline group can also with alkali-free glass fibre on
Coupling agent is reacted, and improves interface binding power and the compatibility of alkali-free glass fibre and heat resistant polyamide 6T/11 resin, fall
The low floating fine probability occurring.
The coupling agent that the present invention adopts, preferably gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane,
All contain amino, and anti-glass emergence on the surface agent N, N'- ethylenebisstearamide contains amide group, above-mentioned auxiliary agent all can be with
The end group of heat resistant polyamide 6T/11 resin reacts, thus improving alkali-free glass fibre and heat resistant polyamide further
The interface binding power of 6T/11 resin and the compatibility, reduce the floating fine probability occurring.
The length of alkali-free glass fibre and diameter are to the mechanical property of heat resistant polyamide 6T/11 resin and appearance effects
Larger.The length of alkali-free glass fibre is bigger, and the tensile property of its resin composite materials is higher, simultaneously the probability of glass emergence on the surface
It is consequently increased；The diameter of alkali-free glass fibre is less, and tensile strength is higher, but the cost of its preparation is higher, unit simultaneously
Coupling agent needed for area is also more.Therefore, select the length of suitable alkali-free glass fibre and diameter excellent to processability
And the high heat resistant polyamide 6T/11 resin combination of cost performance is just particularly important.
The fusing point of double (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamide of N, N'- is 272 DEG C, boiling point is more than
360 DEG C, the better heat stability during heat resistant polyamide 6T/11 resin alloy, its amide group can with high temperature resistant
The end group of polyamide 6 T/11 resin reacts and to improve the compatibility, and hindered piperidine base can provide antioxidation and improve copolymerization
The dyeability of thing.
The fusing point of double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate is 239 DEG C, heat decomposition temperature surpasses
Cross 350 DEG C, there is good thermostability and hydrolytic resistance, can be for providing during heat resistant polyamide 6T/11 resin alloy
Superior colour stability and melt stability, can prevent heat in pyroprocess for the heat resistant polyamide 6T/11 resin simultaneously
Degraded, and inhibit due to the hot oxygen variable color causing for a long time, it also offers in nitrogen oxides (NOx) in the environment of gas
Colour stability, prevent gas from smoking variable color.
Compared with prior art, the invention has the advantages that：
The present invention is not good for the processing temperature narrow limits of existing heat resistant polyamide 6T/11 resin and processing characteristics
Defect, by improving the processability of heat resistant polyamide 6T/11 resin using heat resistant polyamide 6T/11 resin prepolymer
Can, adopt toluene di-isocyanate(TDI) and 2,2'- (1,3- phenylene)-bisoxazoline to solve part heat resistant polyamide simultaneously
6T/11 resin prepolymer makes the excessive defect of the mechanical properties decrease of heat resistant polyamide 6T/11 resin, and adds coupling agent
And N, N'- ethylenebisstearamide is solving the problems, such as floating fibre, compounding use N, double (2,2,6, the 6- tetramethyl -4- piperidines of N'-
Base) -1,3- benzenedicarboxamide and double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate to be processing Blending Processes
In xanthochromia problem, preparation-obtained heat resistant polyamide 6T/11 compositionss have high fluidity, high tensile and low suction
The feature of water rate, can be applicable to field of electronics, LED field, automotive field, Aero-Space and military industry field etc..
Brief description
Fig. 1 show the preparation technology flow chart of heat resistant polyamide 6T/11 compositionss of the present invention.
Specific embodiment
By feature, technological means and the specific purposes being reached, the function of the present invention can be further appreciated that, parse this
Bright advantage and spirit, by following examples, the present invention is further elaborated.
The reaction mechanism of heat resistant polyamide 6T/11 resin combination of the present invention is following, and (preparation technology flow chart asks for an interview figure
1)：
Reaction mechanism
From upper reaction equation, the end of heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin
Amino can react with the isocyanate groups of toluene di-isocyanate(TDI), heat resistant polyamide 6T/11 resin prepolymer and
The Amino End Group of heat resistant polyamide 6T/11 resin, end carboxyl can be with the oxazolines of 2,2'- (1,3- phenylene)-bisoxazoline
Group reacts.The intrinsic viscosity of heat resistant polyamide 6T/11 resin is lower, and its activity is higher, therefore, heat resistant polyamide
The end group of the strand of partly relatively low intrinsic viscosity of 6T/11 resin prepolymer can be distinguished preferential and toluene di-isocyanate(TDI)
There is chain extending reaction in isocyanate groups, the oxazoline group of 2,2'- (1,3- phenylene)-bisoxazoline, improve such pre-polymerization
The intrinsic viscosity of thing is to zone of reasonableness, thus reducing such prepolymer to heat resistant polyamide 6T/11 resin combination mechanical property
The impact of energy, can improve the processing characteristics of resin combination simultaneously again using such prepolymer, thus prepare thering is high stream
The heat resistant polyamide 6T/11 compositionss of dynamic property, high tensile and low water absorption.
The raw material that the embodiment of the present invention is used is as follows：
Heat resistant polyamide 6T/11 resin prepolymer (PA6T/11 prepolymer) and heat resistant polyamide 6T/11 resin
(PA6T/11), make by oneself, the hexamethylene diamine in raw material is selected from Wuxi Yinda Nylon Co., Ltd., p-phthalic acid is selected from Beijing Yanshan Mountain
Petrochemical corporation (complex), 11- aminoundecanoic acid is selected from Taiyuan Zhong Lianze agrochemicals company limited, and remaining auxiliary agent is selected from Chinese medicines group
Learn reagent company limited；
Toluene di-isocyanate(TDI), selected from Chemical Reagent Co., Ltd., Sinopharm Group；
2,2'- (1,3- phenylene)-bisoxazoline, selected from Chemical Reagent Co., Ltd., Sinopharm Group；
Coupling agent (gamma-aminopropyl-triethoxy-silane), selected from Organic Silicon New Material Co. Ltd., Wuhan Univ., Hubei；
Coupling agent (γ-aminopropyltrimethoxysilane), selected from Zhejiang boiling point Chemical Co., Ltd.；
Alkali-free glass fibre, selected from Chinese megalith limited company, length is 3mm, a diameter of 10 μm；
N, N'- ethylenebisstearamide, selected from Guangzhou Bo Han Chemical Co., Ltd.；
Double (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamide of N, N'-, has selected from such as Dong Jinkangtai chemistry
Limit company；
Double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, limited selected from Shanghai point credit fine chemistry industry
Company；
Anti-dripping agent (politef), selected from Minnesota ,USA mines and manufacturing industry company；
Dimethicone, selected from Dow corning company.
To describe the present invention below in conjunction with specific embodiment in detail.
Heat resistant polyamide 6T/11 resin prepolymer in following examples and heat resistant polyamide 6T/11 resin are by list
Body 1 and polyesteramide copolymerization form, and described monomer 1 is 1 for mol ratio：1：0.45～0.55 hexamethylene diamine, p-phthalic acid,
11- aminoundecanoic acid, described polyesteramide addition is the 1～8% of described monomer 1 gross weight, and it has as following formula I structure：
In Formulas I, a=10～200, b=10～200, c=10～100, R is polyesteramide, and it has as Formula Il knot
Structure：
In Formula II, x=10～200, y=10～200, z=10～100.
The synthetic method of heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin is as follows：
(1) the described monomer 1 after vacuum drying is added in stirring-type polymer reactor, is simultaneously introduced described polyamide
Ester, and molecular weight regulator, antioxidant, water；Then evacuation 4～6min, logical nitrogen 4～6min, so circulate 5～7 times,
So that reactant is present in the lower environment of nitrogen protection, control in described stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by airtight for described stirring-type polymer reactor constant-speed heating to 272～280 DEG C, adjust institute
The mixing speed stating stirring-type polymer reactor is 30～50r/min, wherein, when described stirring-type polymer reactor temperature reaches
When 215 DEG C, it is deflated to 2.0MPa, and maintains pressure in 2.0MPa, after reacting 1～2 hour, be deflated to normal pressure, be warming up to simultaneously
After continuing reaction at 310～320 DEG C 1～2 hour, obtain heat resistant polyamide 6T/11 resin prepolymer；
(3) the heat resistant polyamide 6T/11 resin prepolymer that step (2) obtains is continued evacuation at 310～320 DEG C
After 0.3～1 hour, obtain heat resistant polyamide 6T/11 resin；
Described molecular weight regulator is addition is described monomer 1 gross weight 0.1～3% benzoic acid；Described antioxygen
Agent is addition is described monomer 1 gross weight 0.1～0.3% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,
3- benzene diamides；Appropriate amount of water.
Embodiment 1
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step as follows：
(1) by the monomer 1 after vacuum drying：1mol hexamethylene diamine, 1mol p-phthalic acid, 0.5mol 11- aminoundecanoic acid
Be added in stirring-type polymer reactor, be simultaneously introduced 4% polyesteramide of monomer 1 gross weight, 1.5% benzoic acid,
0.2% N, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene diamides, addition 100mL water are as mass-and heat-transfer
Medium；Then evacuation 5min, logical nitrogen 5min, so circulation 6 times, make the environment that reactant is present under nitrogen protection
In, control system pressure in stirring-type polymer reactor to be 0.3MPa；
(2) in 3 hours by airtight for stirring-type polymer reactor constant-speed heating to 275 DEG C, adjust stirring-type polyreaction
The mixing speed of device is 40r/min, wherein, when stirring-type polymer reactor temperature reaches 215 DEG C, is deflated to 2.0MPa, and
Maintain pressure in 2.0MPa, after reacting 1.5 hours, be deflated to normal pressure, be warming up at 315 DEG C after continuing reaction 1.5 hours simultaneously,
Obtain heat resistant polyamide 6T/11 resin prepolymer；
(3) the heat resistant polyamide 6T/11 resin prepolymer that step (2) obtains is continued evacuation 0.5 at 315 DEG C little
Shi Hou, obtains heat resistant polyamide 6T/11 resin；
The intrinsic viscosity of the above-mentioned heat resistant polyamide 6T/11 resin prepolymer preparing is 0.51dL/g, melting temperature
Spend for 290 DEG C, the intrinsic viscosity of heat resistant polyamide 6T/11 resin is 0.86dL/g, melt temperature is 299 DEG C.
A kind of the present embodiment heat resistant polyamide 6T/11 compositionss, are prepared from by the following raw material：
The preparation method of above-mentioned heat resistant polyamide 6T/11 compositionss, comprises the following steps：
(1) described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
After being dried 5 hours, cooling, by the heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, double (the 2,2,6,6- tetramethyl of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-drip
Fall agent (politef) and dimethicone is added in homogenizer and is mixed；
(2) by coupling agent (γ-aminopropyltrimethoxysilane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows：One area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 310 DEG C, 5th area
Temperature is 310 DEG C, and six area's temperature are 310 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 DEG C,
Screw speed is 600rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 35,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 2
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of the present embodiment heat resistant polyamide 6T/11 compositionss, are prepared from by the following raw material：
The preparation method of above-mentioned heat resistant polyamide 6T/11 compositionss, comprises the following steps：
(1) described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
After being dried 5 hours, cooling, by the heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, double (the 2,2,6,6- tetramethyl of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-drip
Fall agent (politef) and dimethicone is added in homogenizer and is mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows：One area's temperature is 260 DEG C, and two area's temperature are 290 DEG C, and three area's temperature are 295 DEG C, and four area's temperature are 300 DEG C, 5th area
Temperature is 300 DEG C, and six area's temperature are 300 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 295 DEG C,
Screw speed is 200rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 50,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 3
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of the present embodiment heat resistant polyamide 6T/11 compositionss, are prepared from by the following raw material：
The preparation method of above-mentioned heat resistant polyamide 6T/11 compositionss, comprises the following steps：
(1) described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
After being dried 5 hours, cooling, by the heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, double (the 2,2,6,6- tetramethyl of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-drip
Fall agent (politef) and dimethicone is added in homogenizer and is mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows：One area's temperature is 285 DEG C, and two area's temperature are 300 DEG C, and three area's temperature are 305 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 305 DEG C, and eight area's temperature are 305 DEG C, and die head temperature is 300 DEG C,
Screw speed is 400rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 45,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 4
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of the present embodiment heat resistant polyamide 6T/11 compositionss, are prepared from by the following raw material：
The preparation method of above-mentioned heat resistant polyamide 6T/11 compositionss, comprises the following steps：
(1) described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
After being dried 5 hours, cooling, by the heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, double (the 2,2,6,6- tetramethyl of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-drip
Fall agent (politef) and dimethicone is added in homogenizer and is mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows：One area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 5
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of the present embodiment heat resistant polyamide 6T/11 compositionss, are prepared from by the following raw material：
The preparation method of above-mentioned heat resistant polyamide 6T/11 compositionss, comprises the following steps：
(1) described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
After being dried 5 hours, cooling, by the heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, double (the 2,2,6,6- tetramethyl of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-drip
Fall agent (politef) and dimethicone is added in homogenizer and is mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows：One area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Embodiment 6
Heat resistant polyamide 6T/11 resin prepolymer used in the present embodiment and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of the present embodiment heat resistant polyamide 6T/11 compositionss, are prepared from by the following raw material：
The preparation method of above-mentioned heat resistant polyamide 6T/11 compositionss, comprises the following steps：
(1) described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
After being dried 5 hours, cooling, by the heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, double (the 2,2,6,6- tetramethyl of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-drip
Fall agent (politef) and dimethicone is added in homogenizer and is mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows：One area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 1
The raw material of the heat resistant polyamide 6T/11 resin used in this comparative example is constituted and the same embodiment of synthesis step
1.
A kind of this comparative example heat resistant polyamide 6T/11 compositionss, are prepared from by the following raw material：
The preparation method of above-mentioned heat resistant polyamide 6T/11 compositionss, comprises the following steps：
(1) described heat resistant polyamide 6T/11 resin is placed in 90 DEG C, after being dried 5 hours, cooling, will be resistance to after cooling
High temperature polyamide 6T/11 resin, and N, double (2,2,6,6- tetramethyl -4- piperidyl) -1, the 3- benzenedicarboxamide of N'-, double (2,
6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone be added to
Mixed in homogenizer；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows：One area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 2
Heat resistant polyamide 6T/11 resin prepolymer used in this comparative example and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of this comparative example heat resistant polyamide 6T/11 compositionss, are prepared from by the following raw material：
The preparation method of above-mentioned heat resistant polyamide 6T/11 compositionss, comprises the following steps：
(1) described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
After being dried 5 hours, cooling, by the heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And N, N'- double (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- methylbenzene
Base) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone be added in homogenizer and mixed
Close；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows：One area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 3
Heat resistant polyamide 6T/11 resin prepolymer used in this comparative example and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of this comparative example heat resistant polyamide 6T/11 compositionss, are prepared from by the following raw material：
The preparation method of above-mentioned heat resistant polyamide 6T/11 compositionss, comprises the following steps：
(1) described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
After being dried 5 hours, cooling, by the heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, double (the 2,2,6,6- tetramethyl of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-drip
Fall agent (politef) and dimethicone is added in homogenizer and is mixed；
(2) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds alkali-free glass fibre to be melt extruded, pelletize, and technological parameter is as follows：
One area's temperature is 290 DEG C, and two area's temperature are 305 DEG C, and three area's temperature are 310 DEG C, and four area's temperature are 315 DEG C, and five area's temperature are 315
DEG C, six area's temperature are 315 DEG C, and seven area's temperature are 310 DEG C, and eight area's temperature are 310 DEG C, and die head temperature is 305 DEG C, and screw speed is
300rpm.
The screw configuration of described parallel double-screw extruder is single thread, and the ratio L/D of spiro rod length L and diameter D is 40,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
Comparative example 4
Heat resistant polyamide 6T/11 resin prepolymer used in this comparative example and heat resistant polyamide 6T/11 resin
Raw material constitute and synthesis step with embodiment 1.
A kind of this comparative example heat resistant polyamide 6T/11 compositionss, are prepared from by the following raw material：
The preparation method of above-mentioned heat resistant polyamide 6T/11 compositionss, comprises the following steps：
(1) described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C,
After being dried 5 hours, cooling, by the heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11 resin,
And toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO), N, double (the 2,2,6,6- tetramethyl of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-drip
Fall agent (politef) and dimethicone is added in homogenizer and is mixed；
(2) by coupling agent (gamma-aminopropyl-triethoxy-silane), alkali-free glass fibre and N,N' ethylene bis stearoyl
Amine is added in another homogenizer and is mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and in parallel pair of spiral shell
Lateral (the 4th area) of bar extruder (totally eight area) adds the mixture that step (2) mixes to be melt extruded, pelletize, technique
Parameter is as follows：One area's temperature is 280 DEG C, and two area's temperature are 295 DEG C, and three area's temperature are 300 DEG C, and four area's temperature are 305 DEG C, 5th area
Temperature is 305 DEG C, and six area's temperature are 305 DEG C, and seven area's temperature are 300 DEG C, and eight area's temperature are 300 DEG C, and die head temperature is 300 DEG C,
Screw speed is 300rpm.
The screw configuration of described parallel double-screw extruder is double thread, and the ratio L/D of spiro rod length L and diameter D is 30,
Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
It is below embodiment and comparative example catalog (table 1)：
Table 1 embodiment forms weight portion catalog with comparative example raw material
Above example and the N of comparative example, double (2,2,6,6- tetramethyl -4- the piperidyl) -1,3- benzenedicarboxamide of N'-,
Double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-dripping agent (politef) and dimethicone
It is respectively 0.15 part, 0.15 part, 1 part, 0.2 part.
The various embodiments described above and comparative example made working of plastics sample are carried out following performance test (result is as shown in table 2)：
Mobile performance：By GB/T 3682-2000 standard testing, 309 DEG C of test temperature, load 1.2kg；
Tensile property：By GB/T 1040.1-2006 standard testing, rate of extension 10mm/min；
Bending property：By GB/T 9341-2008 standard testing, bend speed 10mm/min；
Water absorbing properties：By GB/T 1034-2008 standard testing, testing time 24h.
Table 2 embodiment and comparative example performance catalog
As can be seen that the addition of heat resistant polyamide 6T/11 resin prepolymer is more from embodiment 1～6, its resistance to height
The melt index of warm polyamide 6 T/11 resin combination is bigger, and processing characteristics is better；The addition of alkali-free glass fibre is more,
The tensile strength of its heat resistant polyamide 6T/11 resin combination and bending strength are bigger, but produce floating fine probability simultaneously
Bigger；The water absorption rate change of each embodiment is less.Comprehensive factors above, the combination property of embodiment 6 is optimal.
It is compared with embodiment 6, comparative example 1 is to be not added with the high temperature resistant of heat resistant polyamide 6T/11 resin prepolymer
Polyamide 6 T/11 resin combination, its melt index is only 6g/10min (309 DEG C of test temperature, load 1.2kg), processability
Can not be good；Comparative example 2 be not added with toluene di-isocyanate(TDI) (TDI), 2,2'- (1,3- phenylene)-bisoxazoline (PBO) resistance to
High temperature polyamide 6T/11 resin combination, the heat resistant polyamide 6T/11 resin prepolymer of its partly relatively low intrinsic viscosity is to resistance to
The tensile property of high temperature polyamide 6T/11 resin combination and bending property cause bad impact；Comparative example 3 is to be not added with
Coupling agent, N, the heat resistant polyamide 6T/11 resin combination of N'- ethylenebisstearamide, its heat resistant polyamide 6T/11
The floating fibre phenomenon on resin combination surface increases, and resin combination is not good with the alkali-free glass fibre compatibility, thus to resin group
The tensile property of compound and bending property cause bad impact；The screw configuration of the parallel double-screw extruder of comparative example 4
For double thread, the ratio L/D of spiro rod length L and diameter D is 30, and the screw configuration of the parallel double-screw extruder of embodiment 6
For single thread, the ratio L/D of spiro rod length L and diameter D is 40, by contrast it is found that adopting parallel described in embodiment 6
The Screw Parameters of double screw extruder, the processing characteristics of heat resistant polyamide 6T/11 resin combination that it prepares, stretching
Performance, bending property and water absorbing properties are greatly improved, and obtain the high temperature resistant of high fluidity, high tensile and low water absorption
The beneficial effect of polyamide 6 T/11 resin combination.
Each technical characteristic of embodiment described above can arbitrarily be combined, for making description succinct, not to above-mentioned reality
The all possible combination of each technical characteristic applied in example is all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all it is considered to be the scope of this specification record.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed, but simultaneously
Can not therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
Say, without departing from the inventive concept of the premise, some deformation can also be made and improve, these broadly fall into the protection of the present invention
Scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (10)
1. a kind of heat resistant polyamide 6T/11 compositionss are it is characterised in that be prepared from by the raw material of following weight portion：
The intrinsic viscosity of described heat resistant polyamide 6T/11 resin prepolymer is 0.4～0.6dL/g；
The intrinsic viscosity of described heat resistant polyamide 6T/11 resin is 0.7～1.0dL/g；
Described coupling agent be gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, N- (β-aminoethyl)-γ-
Aminopropyl triethoxysilane, N- β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyl
Methyl dimethoxysilane, γ-aminopropyltriethoxy dimethoxysilane, γ-aminopropyltriethoxy diethoxy silane, anilinomethyl
At least one in triethoxysilane；
The length of described alkali-free glass fibre is 2～4mm, a diameter of 9～11 μm；
Described anti-dripping agent is fluoropolymer.
2. heat resistant polyamide 6T/11 compositionss according to claim 1 are it is characterised in that former by following weight portion
Material is prepared from：
3. heat resistant polyamide 6T/11 compositionss according to claim 1 and 2 are it is characterised in that described high temperature resistant polyamides
The intrinsic viscosity of amine 6T/11 resin prepolymer is 0.45～0.55dL/g；The characteristic of described heat resistant polyamide 6T/11 resin sticks
Spend for 0.75～0.95dL/g.
4. heat resistant polyamide 6T/11 compositionss according to claim 1 and 2 are it is characterised in that described coupling agent is
At least one in gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane；Described anti-dripping agent is polytetrafluoro
Ethylene.
5. heat resistant polyamide 6T/11 compositionss according to claim 1 and 2 are it is characterised in that described high temperature resistant polyamides
Amine 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are formed by monomer 1 and polyesteramide copolymerization, and described monomer 1 is
Mol ratio is 1：1：0.45～0.55 hexamethylene diamine, p-phthalic acid, 11- aminoundecanoic acid, described polyesteramide addition is
The 1～8% of described monomer 1 gross weight.
6. heat resistant polyamide 6T/11 compositionss according to claim 5 are it is characterised in that described heat resistant polyamide
6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are obtained by following synthetic method：
(1) the described monomer 1 after vacuum drying is added in stirring-type polymer reactor, is simultaneously introduced described polyesteramide,
And molecular weight regulator, antioxidant, water；Then evacuation 4～6min, logical nitrogen 4～6min, so circulate 5～7 times, make
Reactant is present in the lower environment of nitrogen protection, control in described stirring-type polymer reactor system pressure for 0.2～
0.3MPa；
(2) in 2～4 hours by airtight for described stirring-type polymer reactor constant-speed heating to 272～280 DEG C, stir described in regulation
The mixing speed mixing formula polymer reactor is 30～50r/min, wherein, when described stirring-type polymer reactor temperature reaches 215
DEG C when, be deflated to 2.0MPa, and maintain pressure in 2.0MPa, after reacting 1～2 hour, be deflated to normal pressure, be warming up to 310 simultaneously
After continuing reaction at～320 DEG C 1～2 hour, obtain described heat resistant polyamide 6T/11 resin prepolymer；
(3) the described heat resistant polyamide 6T/11 resin prepolymer that step (2) obtains is continued evacuation at 310～320 DEG C
After 0.3～1 hour, obtain described heat resistant polyamide 6T/11 resin；
Described molecular weight regulator is addition is described monomer 1 gross weight 0.1～3% benzoic acid；Described antioxidant is
Addition is the N of the 0.1～0.3% of described monomer 1 gross weight, N'- bis- (2,2,6,6- tetramethyl -4- piperidyl) -1,3- benzene
Diamides；Appropriate amount of water.
7. the preparation method of the heat resistant polyamide 6T/11 compositionss described in a kind of any one of claim 1-6, its feature exists
In comprising the following steps：
(1) described heat resistant polyamide 6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 80～100 DEG C,
After being dried 4～12 hours, cooling, by the heat resistant polyamide 6T/11 resin prepolymer after cooling, heat resistant polyamide 6T/11
Resin, and described toluene di-isocyanate(TDI), 2,2'- (1,3- phenylene)-bisoxazoline, N, double (2,2,6, the 6- tetramethyls of N'-
Base -4- piperidyl) -1,3- benzenedicarboxamide, double (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphate, anti-drip
Fall agent and dimethicone is added in homogenizer and is mixed；
(2) described coupling agent, alkali-free glass fibre and N,N' ethylene bis stearmide are added to another homogenizer
In mixed；
(3) compound that step (1) mixes is added in parallel double-screw extruder through feeder, and squeeze in parallel double-screw
Go out the mixture that the lateral addition step (2) of machine mixes, melt extruded, pelletize, technological parameter is as follows：One area's temperature is
260～290 DEG C, two area's temperature are 290～305 DEG C, and three area's temperature are 295～310 DEG C, and four area's temperature are 300～310 DEG C, five
Area's temperature be 300～310 DEG C, six area's temperature be 300～310 DEG C, seven area's temperature be 300～310 DEG C, eight area's temperature be 300～
310 DEG C, die head temperature is 295～305 DEG C, and screw speed is 200～600rpm.
8. preparation method according to claim 7 is it is characterised in that by described heat resistant polyamide in described step (1)
6T/11 resin prepolymer and heat resistant polyamide 6T/11 resin are placed in 90 DEG C, are dried 4～6 hours；Work in described step (3)
Skill parameter is：One area's temperature is 260～285 DEG C, and two area's temperature are 290～300 DEG C, and three area's temperature are 295～305 DEG C, 4th area
Temperature is 300～305 DEG C, and five area's temperature are 300～305 DEG C, and six area's temperature are 300～305 DEG C, and seven area's temperature are 300～305
DEG C, eight area's temperature are 300～305 DEG C, and die head temperature is 295～300 DEG C, and screw speed is 200～400rpm.
9. the preparation method according to claim 7 or 8 is it is characterised in that the screw shaped of described parallel double-screw extruder
Shape is single thread；The ratio L/D of spiro rod length L and diameter D is 35～50；Described screw rod is provided with the gear block area of more than 1
With the left-hand thread area of more than 1.
10. preparation method according to claim 9 is it is characterised in that the ratio L/D of described spiro rod length L and diameter D is 35
～45；Described screw rod is provided with 2 gear block areas and 1 left-hand thread area.
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| CN115961379A (en) * | 2022-12-08 | 2023-04-14 | 杭州汇维仕永盛染整有限公司 | Sea-island fiber fabric and preparation method thereof |
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